KR20190104605A - Coated glass-based articles having engineering stress profiles and methods for manufacturing the same - Google Patents

Abstract

Coated glass-based products and methods for making the same are disclosed. The article has a chemically strengthened glass-based core substrate having a first surface and a second surface, chemically having a third surface directly bonded to the first surface to provide a first core-cladding interface. A chemically strengthened glass-based second cladding substrate having a strengthened glass-based first cladding substrate and a fourth surface directly bonded to the second surface to provide a second core-cladding interface. Wherein the core substrate is coupled to the first cladding substrate and the second cladding substrate, wherein a coating is present on the first cladding substrate.

Description

Coated glass-based articles having engineering stress profiles and methods for manufacturing the same

This application claims 35 U.S.C. Claims priority of US Provisional Application No. 62/447562, filed January 18, 2017, under § 120, which is incorporated herein by reference in its entirety.

Embodiments of the present disclosure generally relate to coated glass-based articles having engineering stress profiles and methods of making the same.

Reinforced glass-based products are cover plates or windows for mobile or mobile telecommunications and entertainment devices such as mobile phones, smartphones, tablets, video players, information terminal (IT) devices, laptop computers, navigation systems, and the like. In electronics as well as construction (eg windows, shower panels, countertops, etc.), transport (eg, automobiles, trains, aircraft, oceangoing vessels, etc.), thinner and with excellent fracture resistance Widely used in other applications such as all applications requiring a lightweight product.

In toughened glass-based products, such as chemically strengthened glass articles, the compressive stress is highest or at the peak at the glass surface, reduced from the peak as it moves away from the surface, and the stress in the glass article is subject to tension. There is a zero stress at some internal location of the glass product before it becomes. Modifications to the ionic process can be used to address the initial flaw population susceptibility in glass-based products to modify the stress profile of the glass to reduce the susceptibility to early flaw populations. While modifications to the ion exchange process can be used for this purpose, as toughened glass-based products are increasingly used, they have improved reliability while not significantly affecting the average strength of the toughened glass-based materials. It would be desirable to develop other methods of providing reinforced glass-based materials. While hard, brittle coatings on the surface of glass-based products can be used to provide scratch resistance for glass-based products, for glass-based products with steep stress profiles, hard coatings have glass with hard brittle coatings. It may have a tendency to lower the bending strength performance of the -based product.

While modifications to the ion exchange process can be used for this purpose, as toughened glass-based products are increasingly used, they have improved reliability while not significantly affecting the average strength of the toughened glass-based materials. It would be desirable to develop other methods of providing reinforced glass-based materials. While hard, brittle coatings on the surface of glass-based products can be used to provide scratch resistance for glass-based products, for glass-based products with steep stress profiles, hard coatings have glass with hard brittle coatings. It may have a tendency to lower the bending strength performance of the -based product.

Aspects of the present disclosure relate to coated glass-based articles wherein a coating having a Young's modulus value is applied to a laminated substrate comprising a core substrate, a first cladding substrate, and a second cladding substrate. The first cladding substrate has a cladding substrate Young's modulus value less than the coating Young's modulus value. Another aspect of the present disclosure relates to a method of making a coated glass-based article disclosed herein.

The accompanying drawings, which are incorporated in and constitute a part of this specification, describe several implementations described below.
1 shows an embodiment of a glass-based substrate having a surface with a plurality of cracks;
2 shows an embodiment of a coated, laminated glass-based article;
3 shows another embodiment of a coated, laminated glass-based article;
4 shows the model stress profile of an uncoated , laminated glass-based article ;
5A shows the model stress profile of an uncoated , laminated glass-based article ;
5B shows the model strength versus defect length for the stress profile of FIG. 5A;
6A shows the model stress profile of an uncoated, laminated glass-based article ;
6B shows the model strength versus defect length for the stress profile of FIG. 6A;
7A shows the model stress profile of an uncoated, laminated glass-based article;
FIG. 7B shows the model strength versus defect length for the stress profile of FIG. 7A; FIG.
8A shows the model stress profile of an uncoated, laminated glass-based article;
FIG. 8B shows the model strength versus defect length for the stress profile of FIG. 8A;
9A shows the model stress profile of an uncoated, laminated glass-based article;
FIG. 9B shows the model strength versus defect length for the stress profile of FIG. 9A; FIG.
10A shows the model stress profile of an uncoated, laminated glass-based article;
10B shows the model strength versus defect length for the stress profile of FIG. 10A;
11 shows the model stress profile of an uncoated, laminated glass-based article;
12 shows the model stress profile of an uncoated, laminated glass-based article;
FIG. 1 shows the model strength for the depth profile of the laminated glass-based product profile of FIG. 12;
14 shows the model stress profile of an uncoated, laminated glass-based article;
FIG. 1 shows the model strength for the depth profile of the laminated glass-based product profile of FIG. 14; FIG.
1A shows the model stress profile of a coated, laminated glass-based article;
Figure 1 6b shows a model intensity for the defect length with respect to the stress profile of Figure 16a;
1A shows the model stress profile of a coated, laminated glass-based article;
FIG. 1 7B shows the model strength versus defect length for the stress profile in FIG. 17A; FIG.
1 8 shows a ring on ring test set-up for measuring the strength of a substrate;
1A is a top view of an exemplary electronic device including all coated-glass based articles disclosed herein; And
19B is a perspective view of the exemplary electronic device of FIG. 19A.

Prior to describing some exemplary embodiments, it should be understood that the present disclosure is not limited to the details of construction or process steps set forth in the following description. The disclosure provided herein may be performed or practiced in various ways and other implementations may be possible.

Throughout this specification, "an embodiment," some embodiments ", various embodiments," one or more embodiments "or" embodiments "refer to particular features, structures, materials, described in connection with this embodiment. Or a characteristic is included in at least one embodiment of the foregoing description, thus, "one or more embodiments", "specific embodiments", "various embodiments", "one" in various places throughout this specification. The appearances of the phrase "embodiment" or "an embodiment" are not necessarily referring to the same embodiment. In addition, certain features, structures, materials, or properties may be combined in any suitable manner in one or more embodiments.

One or more embodiments of the present disclosure provide a coated, glass-based article comprising a glass-based substrate having an engineering stress profile. In at least one embodiment the glass-based article is a laminated glass-based article. In at least one embodiment, a coated glass-based article is provided that includes a designed stress profile that provides resistance to fracture due to deep damage. In one or more embodiments, the coated glass-based article is not bendable. In one or more embodiments, the coating comprises a material having a Young's modulus equal to or higher than the cladding of the laminated, strengthened glass-based substrate. According to one or more embodiments, the coating does not have any residual stress or compressive residual stress. In one or more embodiments, the coating has a tensile stress. If the coating does not have any residual stress, the stress profile is a stress profile obtained by shifting the ion-exchange profile by a certain distance into a laminated glass-based article having a cladding substrate of a glass-based article without any compression. It is provided to be similar to The structure according to the model and preliminary experimental data will have the same average strength while being less sensitive to initial glass defects compared to the original laminated reinforced glass-based substrate. The coating may comprise a multilayer coating. The glass-based substrates may be flat, or they may be bent in one or more directions (eg, x, y and / or z planes) to provide a three dimensional stacked substrate. In one or more embodiments, the laminated glass-based substrate is oriented in at least one direction (eg, x, y and / or z planes). In one or more embodiments, the laminated, glass-based substrate can have a 2.5-dimensional dimension, for example by having an oblique edge. The stress profile of the laminated, glass-based substrate may be symmetric (same on the opposite sides of the glass substrate) or asymmetric (stress profile on one side of the substrate is different from the stress profile on the opposite side of the substrate).

According to one or more embodiments, a coated glass-based product is provided. In one or more embodiments, the laminated glass-based article includes a coating to protect the glass-based article from damage, such as sharp contact induced rupture and surface scratches. In one or more embodiments, one or more coatings can be applied to other functions such as capacitive touch sensors, or other optical qualities. Accordingly, embodiments of the present disclosure relate to glass-based articles having multiple coating layers on glass-based articles. In one embodiment, a multilayer scratch resistant coating (eg, 8-layer scratch resistant coating) having a thickness of approximately 2 micrometers is provided, which may be the only coating or combined antireflective coating, Coatings for matching the refractive indices of the underlying glass-based substrates and coatings, and other functional coatings. High stiffness coatings, i.e. coatings having a relatively high Young's modulus relative to the Young's modulus of the brittle tending cladding, are required for glass-based products with stress profiles to mitigate the strength reduction associated with high stiffness brittle coatings. do. In at least one embodiment the laminated glass-based article is provided to include a designed stress profile that provides resistance to fracture due to deep damage. Bending strength (measured using tests such as ring-on-rings) of glass-based products with high stiffness, brittle coatings is a function of maximum surface stress, and between the coating / glass interface and a depth of 10 to 30 micrometers. The shape of the profile is of interest depending on the shape of the profile. According to one or more embodiments, the laminated glass-based article has a stress profile that exhibits improved bending strength of the coated glass-based article and / or exhibits deep damage induction resistance of the composite product.

Coated glass-based articles are disclosed, which have optimized stress profiles for deep flaws. In some embodiments, the optimized stress profile improves the retention strength for deep defects, for example defects greater than 100 microns, while also having sufficient bending strength due to high compressive stress at the surface. Improve the drop performance of the system. In one or more embodiments, the optimized drop performance is due to a specially designed stress profile that produces high compressive stress in areas where defects due to damage introduction are expected to end. In one or more embodiments, the coated, laminated glass-based article exhibits a compressive stress profile in which more steep tangents (ie, spikes in the stress profile of the surface) are present at or near the surface. The stress profile of one or more embodiments is characterized by the presence of two distinct regions with tangents in one region—one with a relatively steep tangent and one with a shallow tangent.

In one embodiment, the proposed stress profile is a modified ion exchange process, for example two or more ion exchange processes or a combination of two or more other reinforcement mechanisms, e.g., stack strengthening, ion exchange (chemical tempering due to CTE mismatches). ) Or through a combination of thermal tempering. Embodiments of glass-based products are generally less than 2 mm thick and the brittle coating thickness is generally less than 10 micrometers and thicker than 10 nanometers. According to one or more embodiments, the coated glass-based product stress profile may turn out to improve bending strength, deep damage resistance, or both. In certain embodiments, smooth surface drop fracture is controlled by bending strength, so improved resistance to coating defect propagation will also improve smooth surface drop performance. Coated glass-based products with optimized stress profiles and brittle functional coatings are expected to perform better than glass-based products or standard ion-exchanged glass-based products with a depth of layer with the same coating. do.

In one or more embodiments , the optimized stress profile is characterized by a deep flaw (eg, greater than 70 μm, greater than 80 μm, greater than 90 μm to improve mechanical reliability against drop-induced damage as compared to standard single ion exchange reinforcement or lamination. More than 100 μm, more than 110 μm, more than 120 μm, more than 130 μm, more than 140 μm, more than 150 μm, more than 160 μm, more than 170 μm, more than 180 μm, more than 190 μm, more than 200 μm, more than 210 μm, 220 Strength protection of laminated glass-based articles (greater than micrometers, greater than 230 micrometers, greater than 240 micrometers and greater than 250 micrometers) can be significantly increased. In one or more embodiments, the optimized stress profile may also have bending strength behavior that is comparable for shorter defects (eg, less than 10 μm). In one or more embodiments, the optimized stress profile can include deep defects (eg, greater than 70 μm, greater than 80 μm, greater than 90 μm, greater than 100 μm, greater than 110 μm, greater than 120 μm, greater than 130 μm, greater than 140 μm, More than 150 μm, more than 160 μm, more than 170 μm, more than 180 μm, more than 190 μm, more than 200 μm, more than 210 μm, more than 220 μm, more than 230 μm, more than 240 μm, and more than 250 μm). It can be created to provide stress corrosion resistance.

According to one or more embodiments, an optimized stress profile can be achieved through a lamination process followed by a coating process. The profile may be created by laminating glass-based substrates on both sides of a core substrate having an ion exchange profile to provide a laminated stack and then ion exchanging the laminated stack to provide a laminated glass-based substrate. The laminated glass-based substrate has tension on the cladding glass and compression on the core glass as opposed to conventional laminated glass. The relative ion diffusivity of the core and cladding may provide another way of controlling the stress profile of the glass-based article. A coating is applied to the laminated glass based product.

Damage associated with the drop event can cause chipping and densification near the surface of the glass-based substrate, which is consistent with the highest residual compressive stress for the error function profile. According to one or more embodiments, a buried peak profile can be obtained, wherein the stress is buried unaffected by surface damage caused during a drop event on a rough surface.

In one or more embodiments , the compositions of the core and clad glass-based substrates are the same or different, which may enable the integration of new design features and applications. According to one or more embodiments, other compositions of the core and clad glass substrates further increase the deep damage fracture resistance of the glass-based substrate, for example by using a coefficient of thermal expansion (CTE) difference to create compressive stress in the clad layer. It can be used for this purpose, which results in improved rough surface drop performance. In one or more embodiments, the thickness of the clad glass-based substrate can be varied to accurately locate the depth of the buried peak of the stress profile. As used herein, a "embedded peak" referring to a stress profile refers to a local maximum in stress to depth from the surface of the glass, the local maximum or peak being between the outer surface and the embedded peak of the glass-based product. It has a higher magnitude of stress in the axial stress than the point of.

In one or more embodiments, core and clad substrate properties such as ion diffusivity can be selected to precisely control surface residual stress and dispersion of buried peaks in glass-based articles. For example, low ion diffusivity cores and high ion diffusivity clads will result in embedded peaks similar to the standard ion exchange error function profile, however, according to one or more embodiments, the glass articles described herein are Compared to profiles, there is a greater degree of tunability of bending and stress profiles in stress profile designs. Using glass substrates with different ion diffusivities can control the properties of buried peaks such as stress magnitude and CS depth. In one or more embodiments, the sensor layer can be incorporated into an ion exchanged stack of substrates.

In one or more embodiments, there is provided a glass-based article having an optimized stress profile for deep flaws to enhance the drop performance of the cover glass without sacrificing small bending strength and large flaws (less than 10 μm and greater than 75 μm) do. Also provided is a method of obtaining an optimized stress profile for deep flaws in order to improve the drop performance of the cover glass.

In one or more embodiments , a coated, glass-based product is provided having an optimized stress profile for drop, scratch, and warp performance, and a method of producing such a profile is provided. In one embodiment, the optimized profile can be generated through a combination of bonding the thin glass-based cladding substrate to the core substrate by ion exchange and covalent bonding. In one or more embodiments, the method of producing such an optimized profile can include selecting a glass substrate having a predetermined composition to provide a core substrate of a laminated glass-based article. The predetermined composition is selected according to one or more embodiments in terms of several downstream processes that will change the profile size and shape, which will be discussed further below. In one or more embodiments, the core substrate is chemically strengthened and the resulting stress profile is also predetermined in terms of the magnitude of the stress at the surface and the depth of the stress layer. In one or more embodiments, two cladding substrates, ranging in thickness from about 50 to 150 μm, having a predetermined thickness and composition, are bonded to the core substrate. In one or more embodiments, the cladding substrate may be coupled to the core substrate by covalent bonding.

In one or more embodiments , high temperatures to form covalent bonds can cause additional ion diffusion in the ion exchanged core substrate, which will lower the magnitude of the stress and increase the depth of the stress. It is also possible for the sodium and potassium ions in the core substrate to diffuse into the clad glass, but the modeling used herein assumes that the interface between the core and the cladding is non-permeable. After bonding, the entire laminate is again ion exchanged to create compressive stress in the thin cladding substrate. The stress profile will impart bending strength to the laminated glass article. The second ion exchange will reduce the size of the core ion exchange and further increase the depth due to diffusion, and the total energy stored will be maintained.

4 shows various stress profiles in the steps of a process for forming a laminated glass-based article prior to coating in accordance with one or more embodiments. Solid lines represent exemplary stress profiles of chemically strengthened core substrates. Two layers of glass cladding substrates, each having the same thickness and composition, are bonded to the surface of the chemically strengthened core glass substrate. The composition of the cladding glass substrate may be different from the core glass, and the thickness of the cladding glass substrate will generally be thinner than that of the core glass substrate. The entire laminated glass article is then chemically strengthened resulting in an exemplary stress profile as represented by the long dashed line. The thermal process for joining the substrates changes the stress profile of the core glass substrate represented by the solid line with the stress profile represented by the small dashed line due to the non-transmissive boundary layer diffusion. The final stress profile is the overlap of the small dashed line with the ion exchange profile applied to the outer layer. The stress profile includes a first portion 310 having a relatively steep tangent 311 close to the surface at all points and a tangent 321 that is relatively shallow compared to the steep tangent 311 at all points. And a second portion 320. In one or more embodiments, the first portion comprising the steep tangent 311 and the second portion comprising the relatively shallow tangent 321 have a ratio of the steep tangent to the relatively shallow tangent greater than 1 and greater than 2. Greater than 4, greater than 8, greater than 10, greater than 15, greater than 20, greater than 25, greater than 30, or greater than 35 and less than 40. In one or more embodiments, the relatively steep tangent 311 of the first portion has an absolute value in the range of 3 MPa / micron and 40 MPa / micron, and the relatively shallow tangent 321 of the second portion is It has an absolute value in the range of 0.5 MPa / micron and 2 MPa / micron. In some embodiments, the tangent is described as a "local gradient" and can be used interchangeably, which is defined as the change in stress magnitude as a function of depth. Applying a rigid or brittle coating to the laminate having the stress profile shown in FIG. 4 will provide improved bending strength to the laminated glass-based article, as will be further understood below.

In one or more embodiments, the coated glass-based article has a stress profile that does not follow a single complementary error function. The embodiment shown in FIG. 4 is based on a total thickness of 1.0 mm, each having a cladding substrate 100 μm thick and a core substrate 800 μm thick.

In one or more embodiments , the process for bonding the core substrate to the cladding substrate to form a stacked stack may include cleaning the surfaces of the core substrate and the cladding substrate with a high pH solution. For example, what is known as an RCA cleaning or SC1 process can be used. In one or more embodiments, the RCA cleaning process includes removal of organic contaminants (organic cleaning + particle cleaning), removal of thin oxide layers (oxide strips, optional) and removal of ionic contaminants (ion cleaning). The substrate may be dipped in water, such as demineralized water, and rinsed with water between each step. In one or more embodiments, the cleaning may comprise only an SC1 (referred to as a standard cleaning process) process, which is used to remove the substrate from demineralized water and aqueous ammonium hydroxide (eg, 29 weights of NH ₃ ) and hydrogen peroxide (eg For example, 30%). An exemplary SC1 solution may comprise 5 parts (by volume) of water, 1 part of ammonium hydroxide and 1 part of aqueous hydrogen peroxide. The washing step can occur at room temperature (eg, about 25 ° C.) or at elevated temperatures in the range of 50 ° C. to 80 ° C. The substrate may be placed in the solution for 1 to 30 minutes. The solution wash removes organic residues and particles.

According to one or more embodiments, in addition to the SC1 process, an optional oxide strip may be performed. The oxide strip according to one or more embodiments is a water-based HF at a temperature ranging from 25 ° C. to 80 ° C. for a period of time from about 15 seconds to about 5 minutes to remove the thin oxide layer and some fraction of the ionic contaminants. Immersion of hydrofluoric acid in a 1: 100 or 1:50 solution. In one or more embodiments, the third step includes ionic cleaning. In an exemplary embodiment, a solution of water (eg demineralized water), aqueous HCl (eg hydrochloric acid, eg 37% by weight) and aqueous hydrogen peroxide (eg 30% by weight) is provided. Exemplary solutions are 6 parts (volume) of demineralized water, 1 part HCl and 1 part hydrogen peroxide. The substrate is placed in a solution at room temperature (eg, about 25 ° C.), or at elevated temperatures ranging from 50 ° C. to 80 ° C. The substrate may be placed in the solution for 1-30 minutes. This ionic cleaning process effectively removes remaining trace metallic (ionic) contaminants, some of which were introduced in the SC-1 cleaning step. In an optional step, the substrate may be rinsed with water (such as demineralized water) and then placed in a stack and heated at a temperature in excess of about 400 ° C. for about 1 hour at a continuously applied pressure. The resulting laminated glass-based article will comprise a cladding substrate and a core substrate bonded together. After lamination, the entire laminated glass article is ion exchanged to create compressive stress in the thin layer of the cladding substrate. According to one or more embodiments, the resulting stress profile will impart bend strength to the laminated glass-based article. Ion exchange of laminated glass-based articles according to some embodiments will reduce the size of the core ion exchange, further increase the depth due to diffusion, and the total energy stored will be maintained.

As used herein, the terms “glass-based product” and “glass-based substrate” are used to the broadest range, including all objects that are all or partly made of glass. Glass-based articles include lamination of glass and non-glass materials, lamination of glass and crystalline materials, and glass-ceramic (including amorphous and crystalline phases). Unless otherwise specified, all compositions are expressed in mol% (mol%). The glass substrate according to one or more embodiments may be selected from soda lime glass, alkali aluminosilicate glass, alkali containing borosilicate glass and alkali aluminoborosilicate glass. In one or more embodiments, the substrate is glass and the glass can be tempered, for example, heat tempered, tempered glass, or chemically tempered glass. In one or more embodiments, the strengthened glass-based substrate extends in the chemically strengthened glass from the surface of the chemically strengthened glass to a depth layer of compressive stress compression (DOC) of at least 10 μm to several tens of microns deep. It has a compressive stress (CS) layer with CS. In one or more embodiments, the glass-based substrate is a chemically strengthened glass-based substrate such as Corning Gorilla® glass. The various glass-based articles disclosed herein can be selected from architectural glass substrates, vehicle glazings, in-vehicle glass substrates, consumer electronics glass substrates, handheld device glass substrates, and wearable device glass substrates.

It is noted that the terms "substantially" and "about" may be used herein to indicate the degree of inherent uncertainty that may result from any quantitative comparison, value, measurement or other expression. These terms are also used to indicate the extent to which a quantitative expression can be varied from the referenced reference without causing a change in the basic function of the subject matter. Thus, for example, a glass-based article that is “substantially free of MgO” is one in which MgO is not actively added or disposed in the glass-based article, but can be present in very small amounts as a contaminant.

As used herein, DOC refers to the depth at which stresses in glass-based products change compression into tensile stress. In the DOC, the stresses traverse from positive (compression) stress to negative (tensile) stress and thus represent zero stress values.

As used herein, the terms “chemical depth”, “chemical depth of layer”, “depth of layer” and “depth of chemical layer” refer to ions of metal oxides or alkali metal oxides (eg, metal ions or alkalis). Metal ions) and the depth at which the concentration of the ions reaches a minimum value and can be used interchangeably.

As is commonly used in the art, compression is represented as a negative (<0) stress and tensile is represented as a positive (> 0) stress. However, throughout this description, CS is expressed as a positive or absolute value, ie, CS = | CS |, as described.

1 shows an exemplary strengthened glass-based substrate 10 having a plurality of cracks, showing how subsurface damage can result in fracture. The compressive stress region 60 extending from the outer surface 55 of the glass-based substrate 10 to the depth DOC of the compressive stress layer is under compressive stress CS. The crack 50 in the compressive stress region 60 of the exemplary strengthened glass-based substrate 10 that does not extend into the central tensile region 80 of the glass is a crack penetrating into the central tensile region 80 of the glass. Along 90, which is the area under tensile stress or central tension (CT). The incorporation of CS in the near surface region of glass can prevent the fracture and crack propagation of the glass-based substrate, but if the damage extends beyond the DOC, and if the CT is sufficiently high in size, the defect is a material. It will propagate over time until it reaches a critical stress intensity level (breaking toughness) and will ultimately rupture the glass.

Next, referring to FIG. 2, a first embodiment of the present disclosure relates to a glass-based product 200, which is about 0.1 millimeters facing the first surface 228 and the first surface 228. A glass-based substrate having a second surface 248 that defines a substrate thickness t in the range of 3 to 3 millimeters, wherein the glass-based substrate extends to a depth of layer 215. It has a compressive region 220 having a first compressive stress CS max at the first surface 228 and a second local CS max at a depth of at least 25 μm from the first surface 228. In one or more embodiments, the glass-based article 200 has a third compressive stress CS max at the second surface 248 of the glass-based substrate 210 extending to the depth of the layer 242 and the It has a second compressive region 240 having a fourth local CS maximum at a depth of at least 25 μm, 50 μm, 75 μm or 100 μm from the second surface 248. In one or more embodiments, the glass-based substrate has a substrate Young's Modulus value. In one or more embodiments, coating 260 is on second surface 228, and coating 260 has a coating Young's modulus value greater than the substrate Young's modulus. The coating 260 has a coating thickness t _co .

In a second embodiment, the glass-based substrate 210 includes a glass-based core substrate 211 having a first side 212 and a second side 214, wherein the glass-based core The substrate 211 is interposed between the glass-based first cladding substrate 221 and the glass-based second cladding substrate 241, and by covalent bonding the first cladding substrate 221 is formed of a first substrate. Coupled to the side 212, the second cladding 241 substrate is coupled to the second side 241. The glass-based article shown in FIG. 2 comprising a core substrate and a first cladding substrate 221 and a second cladding substrate 241 may be referred to as a stacked stack. According to one or more embodiments, a covalent bond refers to a bond which is a molecular bond that is a chemical bond comprising a covalent pair of electron pairs, known as a covalent pair or a bond pair. According to one or more embodiments, the covalent bonds may comprise σ-bonds, π-bonds, metal-to-metal bonds, agostic interactions, vent bonds, and three-point 2-atomic bonds. . In one or more embodiments, the covalent bonds include bonds comprising Si—O—Si bonds.

In a third embodiment, the glass-based article of the second embodiment has a core substrate comprising a first glass composition, wherein each of the first cladding substrate 221 and the second cladding substrate 241 And a second glass composition, wherein the first glass composition is different from the second glass composition. In a fourth embodiment, the glass-based article of the third embodiment has the first glass composition having a first ion diffusivity, each of the second glass compositions having a second ion diffusivity, The first ion diffusivity and the second ion diffusivity are made different from each other. In a fifth embodiment, the glass-based articles of the third and fourth embodiments comprise the first glass composition having a first coefficient of thermal expansion (CTE), wherein each of the second glass compositions is of a second type. It has a coefficient of thermal expansion (CTE), so that the first CTE and the second CTE are different. In a sixth embodiment, the glass-based article of the fifth embodiment causes the second CTE to be lower than the first CTE to impart compressive stress to the first cladding substrate and the second cladding substrate. .

In a seventh embodiment, the glass-based article of the third to seventh embodiments has the core substrate 211 having a first stress profile and the first cladding substrate 221 and the second cladding. Each of the substrates 241 has a second stress profile, where the first stress profile is different from the second stress profile. In an eighth embodiment, the glass-based articles of the third to seventh embodiments have the first glass composition having a first Young's modulus value and the second glass composition having a second Young's modulus value The first Young's modulus value and the second Young's modulus value are different, and the coating Young's modulus value is greater than the second Young's modulus value. In a ninth embodiment, the glass-based article of the eighth embodiment is such that the second Young's modulus value is greater than the first Young's modulus value. In a tenth embodiment, the glass-based article of the eighth embodiment is such that the second Young's modulus value is less than the first Young's modulus value.

In an eleventh embodiment, all glass-based articles of the first through tenth embodiments have a first portion and a tangent in which all of the points are relatively steep at all points in the glass-based article. Compared to the depth from the first surface 228 to provide a stress profile comprising a second portion comprising a relatively shallow tangent compared to. In a twelfth embodiment, the glass-based article of the tenth embodiment is such that the ratio of the steep tangent to the relatively shallow tangent is greater than two. In a thirteenth embodiment, the glass-based article of the eleventh embodiment has a steep tangent having an absolute value in the range of 10 MPa / micron to 20 MPa / micron, wherein the steep tangent is in the range of 0.5 MPa / micron and 2 MPa / micron. To have an absolute value of. In a fourteenth embodiment, all glass-based articles of the first through thirteenth embodiments are such that the coating has a coating thickness t _{co in the} range of about 80 nanometers to 10 micrometers.

In a fifteenth embodiment, all glass-based articles of the first through fourteenth embodiments have a Young's Modulus value in the range of 60 GPa to 80 GPa and the coating has a Young's Modulus value in the range of 70 GPa to 400 GPa To have. In a sixteenth embodiment, all glass-based articles of the first through fifteenth embodiments have the coating Young's modulus values in the range of 100 GPa to 300 GPa. In a seventeenth embodiment, all of the first through sixteenth embodiments further comprise that the coating is Al ₂ O ₃ , Mn, AlO _x N _y , Si ₃ N ₄ , SiO _x N _y , Si _u Al _v O _x N _y , diamond, diamond-like carbon, Si _x C _y , Si _x O _y C _z , ZrO ₂ , TiO _x N _y And a scratch resistant coating selected from the group consisting of a combination thereof.

In an eighteenth embodiment, all of the glass-based articles of the first through seventeenth embodiments provide bending strength to prevent breakage of the glass-based article from defects resulting from the first coating. Have a compressive stress profile with a first maximum compressive stress at a sufficient first surface. In a nineteenth embodiment, the glass-based article of the eighteenth embodiment is such that the first maximum compressive stress is in the range of 800 MPa to 1200 MPa, for example 900 MPa, 1000 MPa, or 1100 MPa.

Next, referring to FIG. 3, a twentieth embodiment of the present disclosure includes a strengthened glass-based core substrate 110 having a first surface 115 and a second surface 135. It relates to a glass-based product (100). In one or more embodiments, the strengthened glass-based substrate 110 is chemically strengthened, or thermally strengthened, or chemically and thermally strengthened. The laminated glass-based article 100 has a chemically strengthened glass-based having a third surface 122 bonded directly to the first surface to provide a first core-cladding interface 125. It further comprises a cladding substrate 120 of 1. The laminated glass-based article 100 is chemically strengthened with a fourth surface 142 bonded directly to the second surface 135 to provide a second core-cladding interface 145. It further comprises a glass-based second cladding substrate 140. In one or more embodiments, the core substrate, the first cladding substrate and the second cladding substrate may be referred to as a stacked stack when they are assembled together. According to one or more embodiments, the core substrate 110 is free of polymer between the core substrate 110 and the first cladding substrate 120 and between the core substrate 110 and the second cladding substrate 140. It is bonded to the first cladding substrate 120 and the second cladding substrate 140 without polymer. Thus, in accordance with one or more embodiments, “directly bonded” refers to the first cladding substrate 120 and the second cladding substrate 140 on the core substrate 110 without additional bonding materials such as adhesives, epoxy, glue, and the like. Indicates the bond to bind. In some embodiments, each of the first cladding substrate 120 and the second cladding substrate 140 is directly bonded to the core substrate 110 by covalent bonding. The first cladding substrate 120 is shown as having a thickness t _c1 , and the second cladding substrate 140 is shown as having a thickness t _c2 , and the core substrate 110 has a thickness of t _s . . The core substrate 110 includes a first glass composition, each of the first cladding substrate 120 and the second cladding substrate 140 includes a second glass composition, and the first glass The composition is different from the second glass composition, wherein the first glass composition has a first Young's modulus value, the second glass composition has a second Young's modulus value, and the glass-based product is Further comprising a first coating 160 on the first cladding substrate, and optionally a second coating 180 on the second cladding substrate 140, wherein the first coating 160 is formed of a first coating 160. A material selected to have a coating Young's modulus value, wherein the first coating Young's modulus value is greater than the second Young's modulus value.

The first cladding substrate 120 is shown as having a thickness t _c1 , the second cladding substrate 140 is shown as having a thickness t _c2 , and the core substrate 110 has a thickness of t _s . . Thus the thickness of the laminated glass-based _article 100 is the sum of t _c1 , t _c2 , and t _s . The first cladding substrate 120 has a fifth surface 128, the second cladding 140 has a sixth surface 148, and the fifth surface 128 and the sixth surface. Surface 148 defines the substrate thickness.

In a twenty-first embodiment, the coated glass-based article of the twentieth embodiment further comprises a second coating 180 on the second cladding substrate 140, wherein the second coating 180 Comprises a material selected to have a second coating Young's modulus value, wherein the second coating Young's modulus value is greater than the second Young's modulus value. In a twenty-second embodiment, the coated glass-based article of the twentieth or twenty-first embodiment is wherein the reinforced core substrate 110 is chemically strengthened and the first cladding substrate 120 is free from deep flaws. It will have a stress profile optimized to be resistant to failure. In a twentythird embodiment, the coated glass-based article 100 of the twenty-second embodiment prevents breakage of the glass-based article from defects in which the first cladding substrate 120 is derived from the first coating. To prevent the fifth surface 128 of the glass-based article 100 having a compressive stress profile with a first maximum compressive stress at a fifth surface sufficient to provide bending strength. In a twenty-fourth embodiment, the first maximum compressive stress is in the range of 500 MPa and 1200 MPa. In a twenty-fifth embodiment, the first maximum compressive stress is in the range of 800 MPa and 1200 MPa, for example 900, 1000, or 1100 MPa.

In a twenty-sixth embodiment, the coated glass-based article of the twenty-fifth to twenty-fifth embodiments has a fifth surface 128 and a sixth surface 148 in a range of about 0.1 millimeters to 3 millimeters prior to coating. To limit the thickness. In a twenty-seventh embodiment, the coated glass-based article of the twenty-sixth to twenty-sixth embodiments allows the first coating 160 to have a thickness in the range of 5 nanometers and 5 micrometers. In a twenty-eighth embodiment, the coated glass-based article of the twenty-second to twenty-sixth embodiments is such that the first coating 160 has a thickness in the range of 10 nanometers to 2 micrometers.

In a twenty-ninth embodiment, the coated glass-based article of the twenty-second to twenty-eighth embodiment wherein the first coating consists of silica, indium tin oxide, aluminum oxynitride, porous silica, glass-ceramic or ceramic To be selected from the group. In a thirtieth embodiment, the coated glass-based article of the twenty to twenty-ninth embodiment is such that the glass-based substrate comprises an alkali exchangeable alkali aluminosilicate glass composition, and in the thirty-first embodiment, the glass The composition is an ion exchangeable alkaline aluminoborosilicate glass composition. In a thirty-second embodiment, the coated glass-based article of the twenty to thirtieth embodiments is selected such that the first cladding thickness promotes stable crack growth for cracks in the range of 25 and 150 microns.

A thirty-third embodiment relates to a method of making a coated glass-based article, the method comprising bonding a glass-based first cladding substrate to a first side of a reinforced glass-based core substrate The cladding substrate of 1 has a first cladding substrate Young's modulus value; Covalently bonding a glass-based second cladding substrate to a second side of the strengthened glass-based core substrate; Chemically strengthening the first cladding substrate and the second cladding substrate; And applying a coating having a coating Young's modulus value to the first cladding substrate, wherein the coating Young's modulus value is greater than the first cladding substrate Young's modulus value. In a thirty-fourth embodiment, the thirty-third embodiment is performed after the glass-based core substrate is chemically strengthened, and after the chemical strengthening of the first cladding substrate is bonded to the core cladding substrate, Chemically strengthening the second cladding substrate is to be performed after bonding the second cladding substrate to the core substrate. In a thirty-fifth embodiment, the thirty-third or thirty-fourth embodiment wherein the core substrate has a first bonding surface and a second bonding surface facing the first bonding surface, wherein the first cladding substrate Said third cladding substrate having a fourth bonding surface, said method comprising said first bonding surface, said second bonding surface, said third bonding surface, and said fourth bonding surface; Cleaning the core substrate, the first cladding substrate and the second cladding substrate to provide a hydroxyl on a surface; Positioning the first bonding surface to be in contact with the third bonding surface and bonding the third bonding surface to be positioned with the fourth bonding surface to provide a stacked stack. In a thirty-sixth embodiment, the thirty-fifth embodiment includes heating the laminate stack, and in the thirty-seventh embodiment, heating the laminate stack comprises: a first bond surface and a third Heating to a temperature and for a time sufficient to form a covalent bond between the bonding surfaces and a covalent bond between the second and fourth bonding surfaces, wherein the covalent bonds are free of polymer or adhesive. Is formed. In a thirty-eighth embodiment, heating the lamination stack comprises heating the lamination stack to at least about 400 ° C. for a period of at least 30 minutes. In a thirty-third embodiment, the thirty-third to thirty-eighth embodiment includes chemically strengthening the first cladding substrate and the second cladding substrate.

Two exemplary profiles of uncoated glass-based substrates according to embodiments of the present disclosure are shown in FIG. 5A. The stress profiles provided in this figure were simulated using defined elemental modeling and rupture mechanisms. In this simulation, the residual stress profile was applied to the glass-based article, cracks were explicitly inserted, and four-point bending was applied to the geometry with surface cracks on the tensile side of the glass-based article. , The stress intensity factor was calculated using a focused mesh approach. Next, the strength of the plate at plane strain as a function of defect size is shown. Two possible profiles generated by bonding a 50 μm clad on an 800 μm substrate are shown in FIG. 5A.

The initial ion exchange profile of the core substrate is selected based on the understanding that the bonding and second ion exchange steps will reduce the size of the CS of the core glass substrate at the surface and also increase the depth. While not wishing to be bound by any theory, it is expected that a single ion exchange (eg, potassium to sodium ions) will impart desired stress profile properties, although further optimization of the profile may be performed. In embodiments in which the modification of the initial ion-exchange profile of the core substrate that occurs during the bonding and ion-exchange of the stack stack is minimized, then a glass with high diffusivity for potassium ions is selected for the core glass-based substrate. In one embodiment, the high diffusivity glass contains lithium. The high diffusivity glass for the cladding substrate is chosen to reduce the time of ion-exchange of the ion exchange of the stack. The resulting stress profile according to one or more embodiments is of sufficient magnitude at the correct depth to prevent deep damage induced during drop events consistent with global device warpage and to capture most of the damage. In one or more embodiments, additional heat treatment can be applied to increase the core stress profile, and in some embodiments the depth of the cladding substrate.

Thus, according to one or more embodiments, the glass-based article provides various methods for tuning the stress profile of the glass-based article by providing a high degree of stress profile tunability. Parameters that can be varied to adjust the final stress profile of the glass-based article include the stress profile shape of the core glass substrate, the thermal processing threshold and the thickness of the cladding substrate. In one or more embodiments, the clade substrate thickness determines the onset of embedded CS. In one or more embodiments, ion exchange of the laminated glass stack is cut to provide sufficient resistance to bending and drop strength from dropping. Further, according to one or more embodiments, ion exchange spikes may be applied to the surface to impart the desired bending strength. Ion exchange of the laminated glass can also be chopped to provide scratch resistance.

FIG. 5B demonstrates the retention strength predictions for the two samples of FIG. 5A, which are 50 to 200 when the stress profile shown in FIG. 5A is compared to the two possible, approximately parabolic, depths of stress of the profile (DOC). It can be shown to have an increased strength for defects of μm. Ion exchange profiles 1 (solid line) and profile 2 (short dashed line) of the core glass substrates are profile 1 laminated articles with 50 μm cladding (long dashed line) and profile 2 laminates with 50 μm cladding (solid line with increased strength) Appear to have a lower strength than the finished product. The increased strength profile for the laminated article exceeds two times the ion exchange profile strength currently available for some defect depths.

Profiles created with 75 μm, 100 μm, and 125 μm cladding substrates are shown in FIG. 6A for two different stress profiles on the core glass substrate, and the retention strength predictions are shown in FIG. 6B for the uncoated glass-based article. Indicates. The lines of the classified ion exchange profile 1 and ion exchange profile 2 are the core glass substrate stress profiles before applying the cladding substrate to form the ion stack and the stack of the stacked stack. Increasing the cladding substrate thickness may generally reduce the maximum strength for defects between 100 and 200 μm, and may also appear to result in increased strength for all defects greater than 200 μm. Thus, the laminated glass-based product stress profile can be finely tuned to provide maximized strength protection against defects that can be induced during drop events on rough surfaces. For all simulations, the core thickness decreases as the cladding thickness increases to maintain a total thickness of 1.0 mm.

In one or more embodiments , other compositions for the core substrate and the cladding substrate may also cause the stress properties of the laminated glass-based article to be embossed to optimize performance for specific applications, such as drop protection against impact on rough surfaces. Can be. The compositions of the core substrate and the cladding substrate are independent of each other, which can provide a wide range of mechanical properties such as CTE and elastic properties. Changing the CTE of the core substrate and the cladding substrate provides a residual stress difference resulting from cooling that will cause compression in either the core or the clad. For example, stresses due to CTE differences between the cladding substrate and the core substrate reduce the elastic energy stored in the glass while providing the same performance. In one or more embodiments, varying the Young's modulus of the core substrate and the cladding substrate may also be performed. 7A-B through 9A-B provide examples of uncoated glass-based articles.

In FIG. 7A, an exemplary profile created to have two 75 μm thick cladding substrates and a total thickness of 1.0 mm compares two ion exchange profiles. Increasing the Young's modulus of the cladding substrate from 70 GPa to 80 GPa and decreasing the core Young's modulus from 70 GPa to 60 GPa results in a significant increase in the strength of all defects beyond the core / clad interface. As shown in FIG. 7B, it was found that the retention strength is increased for defects ending in the core compared to the case where both the core and the clad have a modulus of 70 GPa due to the inconsistency of the modulus. The Young's modulus values disclosed herein are described as measured by the general type of acoustic resonance technique described in ASTM E1875-13 of the name, “Kinetics Young's Modulus by Acoustic Resonance, Shear Modulus, and Poisson's Ratio”.

FIG. 8A shows an exemplary profile created to have two 100 μm thick cladding substrates and a total thickness of 1.0 mm compared to two opposing ion exchange profiles. As shown in FIG. 8B, the retention strength is shown to demonstrate the effect of changing the Young's modulus of the core substrate and the cladding substrate. In this exemplary case, the core substrate Young's modulus was 60 GPa, while the cladding substrate Young's modulus was 80 GPa. Due to the mismatch in Young's modulus, the retention strength was found to be increased for defects terminated in the core compared to the case where both the core substrate and cladding substrate had a Young's modulus of 70 GPa.

In FIG. 9A, an example profile producing two 125 μm thick cladding substrates and a total thickness of 1.0 mm compares two possible ion exchange profiles. As shown in FIG. 9B, the core substrate Young's modulus was 60 GPa, while the cladding substrate Young's modulus was 80 GPa. Due to the Young's modulus mismatch, the retention strength was increased for defects terminated in the core compared to the case where both the core and the clad had a Young's modulus of 70 GPa. 8-10 illustrate additional mechanisms for increasing the damage resistance of laminated glass articles due to deep damage, in addition to the manner of tuning and optimizing stress profiles for finished laminated glass articles. Prove that it is provided.

The flow of ions at the interface between the core substrate and the cladding substrate is not illustrated in FIGS. 8-10. It may be possible for ions in the core to diffuse into the cladding and vice versa. The several profiles of FIGS. 8-10 have a small amount of tension at the boundaries of the cladding that can result in subcritical crack growth for at least some crack lengths. In addition, tensile results in a pronounced dip in retention strength. Longer and deeper ion exchange of the cladding substrate will address each of these issues as long as the longer and deeper ion exchange will remove tension.

Furthermore, by more careful selection of the core and clad composition and the ion-exchange parameters, the profiles as shown in FIG. 10A can be divided into two cladding substrates each having a thickness of 100 μm and laminated glass having a total thickness of 1.0 mm. For system products, examples of embedded peak profiles are provided. The buried peaks differ from the buried peak profiles generated through double ion exchange of a single substrate, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 It may be very deep, greater than 100 μm, 100 μm, 125 μm, or 150 μm. The retention strength plots are shown in FIG. 10B, demonstrating results similar to the examples shown above. However, the illustration also demonstrates the rise-R-curve behavior associated with increased strength for cracks with crack growth less than 100 microns, which results in a stable crack growth as well as a tighter reliability distribution of strength. Thus, the lamination process provides a platform for creating such engineering stress profiles with unique properties. The embedded peak profile has strength advantages over the comparative profile up to 175 μm, and the depth and size to be differentiated can be adjusted to suit the application through the parameters of ion exchange and clad thickness.

In addition, the processes described herein to form laminated glass-based products can be used to integrate sensors or other features into laminated glass-based products, which produce cover glass for electronic devices such as mobile phones and tablets. Useful for Sensors can be beneficial by bringing them closer to the surface of the glass, but thinner cover glass can compromise strength. Integrating the sensor into the cover glass can thus address the purpose of the position of the sensor in proximity to the glass surface without compromising the strength of the cover. To do this, the touch sensor is deposited on a glass substrate. Once the sensor is deposited on the substrate, silica is deposited on the surface of the sensor. Alternatively, if the sensor material has sufficient silicon-oxygen bonds to produce strong covalent bonds with the clad at a bond temperature of 400 ° C., then a silica deposition step on the sensor would not be required. Next, all the components are joined together through a heating process of the stacked stack to form a covalent bond as described herein, but the sensor and the clad are bonded to one side, only the clad is bonded to the other side. This process is advantageous if the sensor can withstand a temperature of approximately 400 ° C. In addition to the sensor, all other functional layers such as light waveguides and photochromic layers can be protected in this manner.

According to one or more embodiments, an alternative method (described as another CTE method) for producing a laminated glass-based article includes a lamination process followed by a deep ion exchange process. In one embodiment, the laminated glass-based product is manufactured using a laminated melting process, as described in US Patent No. 20160114564A1. In this process, the laminated melt draw apparatus for forming the laminated glass article includes an upper isopipe positioned over the lower isopipe. The upper isopipe includes a trough from which the molten glass cladding composition is injected from the dissolution apparatus. Similarly, the lower isopipe includes a trough from which the molten glass core composition is injected from the dissolution apparatus. In this embodiment, as described herein, the molten glass core composition has an average core thermal expansion coefficient CTE _core lower than the average cladding coefficient of thermal expansion CTE _clad of the molten glass cladding composition for the laminated glass-based article, wherein The CTE of the cladding is higher than the core, so that the clad is in tension after cooling to room temperature. Next, the laminated glass-based article is ion exchanged. An example of the profile produced by this process is shown in FIG. 11 for an uncoated glass-based article, which represents the stress profile of laminated glass and deep ion exchange. The laminated glass is made with a stress profile of diamond curves. The cladding is under tension and the core is under compression, which is the opposite of conventional laminated glass. Following the lamination process, a deep ion exchange process is performed. The residual stress from the ion exchange process is a square curve. The final residual stress is the sum of the two stresses from lamination and ion exchange. For lamination, the CTE of the cladding is higher than the core, so the cladding is under tension after cooling to room temperature.

In FIG. 11, the residual stress of the final product was estimated to be the sum of the lamination and ion exchange stresses. In this embodiment, the cladding thickness is 0.12 mm and the thickness of the laminated glass is 1.0 mm. The depth of the compressive layer is increased to about 166 um to 200 um or more. This is greater than a 30 um increase and can improve the retention strength of the material for deep flaws.

According to one or more embodiments, the glass-based article laminated as described above can be used as cover glass for mobile electronic devices such as mobile phones and tablets. The stress profile of the cladding substrate, which is between 65 um and 80 um thick and the laminated glass-based article having a total thickness of 0.4 mm, is shown in FIG. 12 for an uncoated glass-based article. The solid curve is the residual stress from ion exchange (non-lamination) and the dashed curve is the final residual stress due to the linear sum of the lamination and ion exchange stresses. The depth of the compressive layer is almost increased from 65 um to 80 um.

The retention strength of the stress profile of FIG. 12 is shown in FIG. 13, which represents a non-monotonic retention strength with a flaw size for the laminated sample. This is compared with the retention strength of the non-laminated glass indicated by the solid line. In this case, the retention strength is greater when the defect size is deeper than 80 um. It is advantageous if deep defects, for example 100 um, are introduced into the laminated cover glass with undesirable events, for example falling onto a hard surface. To break the glass at twice the bending stress, 200 MPa. You will need 100 MPa. The central tension in the lamination case is reduced, which means that some combination of the compressive stress magnitude and depth of the layer will be increased before the central tension coincides with the non-lamination case, which will improve deep damage performance. Once this is done, the performance benefits of the stacked profile will be further increased compared to the non-laminated profile.

Another embodiment is shown in FIGS. 14 and 15 for a thin, non-coated glass-based article having a total thickness of 0.3 mm, a 50 μm thick cladding substrate. The advantages of the depth of the compression layer and the retention strength at deep flaws are similar to the 0.4 mm glass described above. The depth of the compression layer is almost increased from 60 um to 75 um. There is a better retention strength in nearly 20% increase in depth of the compression layer and deep defects above 70 um. For constant clad thickness and tension, the energy balance indicates that the central compression is inversely proportional to the core thickness, so as the core thickness increases the benefits of the proposed alternative method decrease.

Figure 16a is a coated glass according to an embodiment of the substrate - the stress profile of the system board. For comparison, three different potential ion exchange profiles are shown. Profile 3 (solid line) and Profile 3 (dashed line) are control profiles. The advantage of applying the coating profile is evident from profile 2 (dashed line), which shows that high Young's modulus coatings (greater than Young's modulus of the cladding substrate) increase the compressive stress at the surface of the glass substrate. Comparing profile 3 to the uncoated profile in FIG. 5B, it is demonstrated that higher Young's modulus coatings provide an increase in CS at the surface of the glass article, which results in higher bending strength. The cladding substrate profile estimates a 1.0 mm substrate, while the standard ion exchange profile estimates a 0.8 mm cladding substrate thickness. FIG. 16B shows the retention strength plot for the stress profile in FIG. 16A, which indicates that the profile is created with both high bending strength (high maximum critical strain) and deep scratch resistance to defects between 50 and 180 μm. Prove it. 16B shows that sharper compressive stress is required at the surface to resist cracking from the coating, which improves bending strength.

In FIG. 17A, profile 1 and profile 2 are control profiles, and profile 3 shows the stress profile for the coated laminated glass-based article in which the thermal diffusivity of the clad is higher than the core. 17B shows the resulting retention strengths for these profiles, demonstrating the significant advantages of profile 3 for defects smaller than 180 μm compared to two possible, approximate parabolic deep depth (DOC) profiles. 17A-17B, the coating was estimated to be a single layer with a thickness of 2 μm and a Young's modulus of 225 GPa. Coated glass substrates are known to be destroyed by two different modes: introducing damage during rough surface drops, and flexural failure during smooth surface drops. For uncoated glass, flexural failure without damage introduction is rarely observed due to very high strength retention for short defects (less than 20 μm). However, due to the strength reduction associated with the glass after the application of the hard coating, the device drop on the smooth surface may be in critical failure mode. The flexural failure mode is controlled by the maximum critical strength (or strain), which can be seen in FIG. 17B. Maximum critical strain is a function of both residual stress distribution and size over nearly 5-20 μm. A larger size over the entire distribution is advantageous but not just the peak size. The 50 μm clad profile 2 shown in FIGS. 17A and 17B has advantageous bending strength, while the 50 μm clad profile 1 is worse than the more conventional ion exchange profile due to the higher stress at the surface. According to an embodiment of the present disclosure, it is therefore possible to have bending strength and deep damage resistance from the same profile.

According to one or more embodiments, the increase or decrease in strength on one side of the glass-based substrate can be determined using an abraded ring on ring test. The strength of a material is defined as the stress at which rupture occurs. The wear ring on ring test is a surface strength test for testing flat glass specimens and is described herein by ASTM C1499-09 (2013) under the name "Standard Test Method for Forging Biaxial Equivalent Bending Strength of Modern Ceramics at Ambient Temperature". Wear ring-on ring serves as the basis for the test morphology. The contents of ASTM C1499-09 are incorporated herein by reference in their entirety. In one embodiment, the glass specimen is a method and apparatus as described in Appendix A2 of ASTM C158-02 (2012), entitled “Grinding Process,” under the name “Standard Test Method for Strength of Glass by Bending (Determination of Rupture Coefficient)”. Wear is performed prior to the ring-on-ring test with 90 grit silicon carbide (SiC) particles delivered to the glass sample. The content of ASTM C158-02 and the content of Appendix 2 are specifically incorporated herein by reference in their entirety.

Prior to the ring-on-ring test, the surface of the glass-based product was subjected to ASTM C158-02, in order to remove and / or standardize the surface bonding conditions of the sample using the apparatus shown in Figure A2.1 of ASTM C158-02. Polished as described in Appendix 2. The abrasive material is typically sandblasted onto the surface 110 of the glass-based article at a load of 15 psi using air pressure of 304 kPa (44 psi). After the air flow is established, 5 cm ³ of abrasive material is introduced into the funnel and the sample is sandblasted for 5 seconds after the introduction of the abrasive material.

In the wear ring on ring test, a glass-based article having at least one polished surface 410 as shown in FIG. 18 is also shown as shown in FIG. 18, with biaxial equivalent bending strength (ie, between two concentric rings). Is placed between two concentric rings of different sizes to determine the maximum stress the material can sustain when it is subjected to bending. In the wear ring on ring structure 400, the polished glass-based product 410 is supported by a support ring 420 having a diameter D2. Force F is applied by a load cell (not shown) to the surface of the glass-based article by a load ring 430 having a diameter D1.

The ratio D1 / D2 of the diameter of the load ring and the support ring may range from about 0.2 to about 0.5. In some embodiments, D1 / D2 is about 0.5. The load and support rings 130 and 120 should be aligned concentrically within 0.5% of the support ring diameter D2. The load cell used for the test shall be accurate to within ± 1% of all loads within the selected range. In some embodiments, the test is performed at a temperature of 23 ± 2 ° C. and a relative humidity of 40 ± 10%.

In a stationary design, the radius r of the projecting surface of the load ring 430, h / 2 ≦ r ≦ 3h / 2, where h is the thickness of the glass-based product 410. The load and support rings 430, 420 are typically made of hardened steel with a hardness of HRc > 40. Wear ring on ring fixation is commercially available.

The intended failure mechanism for the wear ring on ring test is to observe the rupture of the glass-based product 410 originating from the surface 430a in the load ring 430. Fractures occurring outside of this area—ie, the load ring 430 and the support ring 420—are omitted in the data analysis. However, due to the thickness and high strength of the glass-based article 410, large deflections of more than ½ of the specimen thickness h are often observed. Thus, it is not common to observe a high percentage of fractures originating from below the load ring 430. The stress cannot be calculated accurately without knowledge of the stress evolution both on the inside and below the ring (collected through the strain gauge analysis) and the origin of the break in each specimen. Thus, the wear ring on ring test is concentrated on the peak load of failure depending on the response measured.

The strength of the glass-based article depends on the presence of surface defects. However, since the strength of the glass is based on original statistics, the possibility of defects of a given size present cannot be accurately predicted. Thus, the probability distribution can generally be used as a statistical representation of the data obtained.

Glass-based articles described according to one or more embodiments may have a variety of end uses. In one or more embodiments, such glass-based products include architectural glazing, automotive windscreens and glazings. According to one or more embodiments, opposing surfaces of the glass-based article may be designed and embossed to have the desired strength and reliability. Similar considerations apply to architectural glazings used in architectural structures.

According to one or more embodiments, the defect size can be determined using microscopy, as follows. Defect sizes can be determined using microscopy by using ASTM standards: four-point bending strength (ASTM C1161: standard test method of bending strength of modern ceramics at ambient temperature) or ring-on-ring test (ASTM C1499-15). C1322-15 (standard practice for microscopic observation and characterization of the origin of rupture in modern ceramics) to determine defect size (origin size) for broken samples. This establishes the defect size distribution for the glass sheet in this application. The more samples used in the failure test, the better the confidence in the defect size distribution data from the test. Alternatively, according to one or more embodiments, the defect size can be determined using strength test and rupture mechanism analysis. In one embodiment, the strength data is obtained using as many samples as feasible using suitable strength tests (four point bending for edge strength and ring-on-ring for internal strength). Appropriate burst analysis models (analytical or finite element analysis) can be used to assess the defect size that causes fracture of the sample in the strength test. It estimates specific defect sizes, shapes, and locations, and this approach is not as accurate as the microscopic approach, but it is easy to establish a defect population.

The strengthened glass-based substrate can be provided using a variety of different processes. For example, exemplary glass-based substrate formation methods include float glass processes and down-draw processes such as melt draw and slot draw. Glass-based substrates made by a plot glass process can be characterized by smooth surfaces, and uniform thicknesses are made by molten glass on a layer of molten metal, typically tin. In one embodiment process, the molten glass injected onto the surface of the molten tin layer forms a floating glass ribbon. As the glass ribbon flows along the tin bath, the temperature is gradually reduced until the glass ribbon solidifies into a solid glass-based substrate that can be lifted from the tin on the rollers. Upon exiting the bath, the glass-based substrate can be further cooled and annealed to reduce internal stress.

Down-draw processes produce glass-based substrates having a uniform thickness with a relatively original surface. Since the average bending strength of glass-based substrates is controlled by the amount and size of surface defects, the original surface with minimal contact has a higher initial strength. If the high strength glass-based substrate is then further strengthened (eg, chemically), the resulting strength may be higher than that of the glass-based substrate having a surface that is wrapped and polished. Down-drawn glass-based substrates may be drawn to a thickness of less than about 2 mm. Furthermore, down drawn glass-based substrates have a very flat and smooth surface that can be used for final applications without costly grinding and polishing.

The melt drawing process uses, for example, a drawing tank having a channel for receiving molten glass raw material. The channel has a weir that opens on top along the length of the channel on both sides of the channel. When the channel is filled with molten material, the molten glass overflows the beam. Due to gravity, the molten glass flows down the outside of the drawing tank according to two flowing glass films. The outside of the drawing tank extends down and inside to merge at the edge below the drawing tank. Two flowing glass films are joined at the edges to melt to form a single flowing glass-based substrate. The melt draw method provides the advantage that the two glass films flowing over the channel melt together, so that the outside of the resulting glass-based substrate is not in contact with any part of the device. Thus, the surface properties of the melt drawn glass-based substrate are not affected by this contact.

The slot drawing process is distinguished from the melt drawing method. In a slow drawing process, the molten raw material glass is provided to a drawing tank. The bottom of the drawing tank has an open slot with a nozzle extending the length of the slot. The molten glass flows through the slot / nozzle and draws downward into the anneal region as a continuous substrate.

In some embodiments , the composition used for the glass-based substrate is at least one clarification selected from the group comprising Na ₂ SO ₄ , NaCl, NaF, NaBr, K ₂ SO ₄ , KCl, KF, KBr, and SnO ₂ And 0-2 mol%.

Once formed, the glass-based substrate may be strengthened to form a strengthened glass-based substrate to provide a reinforced substrate. It should be noted that the glass ceramic substrate can also be reinforced in the same manner as the glass-based substrate. As used herein, the term “reinforced substrate” refers to a glass-based substrate or glass that is chemically strengthened through ion-exchange of larger ions for smaller ions on the surface of the glass-based or glass substrate. Mention may be made of the substrate. However, as mentioned above, thermal strengthening methods well known in the art, such as thermal tempering or heat strengthening, can be used to form a strengthened glass substrate. In some embodiments, the substrate can be strengthened using a combination of chemical strengthening processes and thermal strengthening processes.

In a strengthened glass-based substrate, there is a stress profile in which the compressive stress (CS) on the surface and the tension (center tension, or CT) at the center of the glass are present. According to one or more embodiments, the glass may be thermally strengthened, chemically strengthened or a combination of thermally strengthened and chemically strengthened. As used herein, "thermally strengthened" refers to heat treatment to improve the strength of the substrate, and "thermally strengthened" refers to tempered substrates and heat-reinforced substrates, such as tempered glass. And heat-strengthened glass. Tempered glass includes an accelerated cooling process, which produces higher surface compression and / or edge compression in the glass. Factors affecting the degree of surface compression include air-quenching temperature, volume, and other variables that produce at least 10,000 pounds of surface compression per square inch (psi). Tempered glass is typically four to five times stronger than annealed or untreated glass. Heat-strengthened glass is produced by cooling more slowly than tempered glass, which results in lower compressive strength at the surface, which is approximately twice as strong as annealed or untreated glass.

Examples of glass that can be used for the core and cladding substrates can include alkali aluminosilicate glass compositions or alkali aluminoborosilicate glass compositions, but other glass compositions are also contemplated. Such glass compositions may be characterized as ion exchangeable. As used herein, “ion exchangeable” means that a substrate comprising the composition can exchange cations located at or near the surface of the substrate with cations of the same valence that are larger or smaller in size. It means to be. Glass compositions of one embodiment include SiO ₂ , B ₂ O ₃ and Na ₂ O, wherein (SiO ₂ + B ₂ O ₃ ) ≧ 66 mol. %, And Na ₂ O ≧ 9 mol. %to be. In some embodiments, suitable glass compositions further comprise at least one K ₂ O, MgO, and CaO. In certain embodiments, the glass composition used in the substrate comprises 61-75 mol.% SiO ₂ ; 7-15 mol.% Al ₂ O ₃ ; 0-12 mol.% B ₂ O ₃ ; 9-21 mol.% Na ₂ O; 0-4 mol.% K ₂ O; 0-7 mol.% MgO; And 0-3 mol.% CaO.

Additional Examples Suitable Glass Compositions for Substrates include: 60-70 mol.% SiO ₂ ; 6-14 mol.% Al ₂ O ₃ ; 0-15 mol.% B ₂ O ₃ ; 0-15 mol.% Li ₂ O; 0-20 mol.% Na ₂ O; 0-10 mol.% K ₂ O; 0-8 mol.% MgO; 0-10 mol.% CaO; 0-5 mol.% ZrO ₂ ; 0-1 mol.% SnO ₂ ; 0-1 mol.% CeO ₂ ; Less than 50 ppm As ₂ O ₃ ; And less than 50 ppm Sb ₂ O ₃ ; Where 12 mol.% ≦ (Li ₂ O + Na ₂ O + K ₂ O) ≦ 20 mol.% And 0 mol.% ≦ (MgO + CaO) ≦ 10 mol.%.

Another example glass composition suitable for a substrate includes: 63.5-66.5 mol.% SiO ₂ ; 8-12 mol.% Al ₂ O ₃ ; 0-3 mol.% B ₂ O ₃ ; 0-5 mol.% Li ₂ O; 8-18 mol.% Na ₂ O; 0-5 mol.% K ₂ O; 1-7 mol.% MgO; 0-2.5 mol.% CaO; 0-3 mol.% ZrO ₂ ; 0.05-0.25 mol.% SnO ₂ ; 0.05-0.5 mol.% CeO ₂ ; Less than 50 ppm As ₂ O ₃ ; And less than 50 ppm Sb ₂ O ₃ ; Where 14 mol.% ≦ (Li ₂ O + Na ₂ O + K ₂ O) ≦ 18 mol.% And 2 mol.% ≦ (MgO + CaO) ≦ 7 mol.%.

In certain embodiments, suitable alkali aluminosilicate glass compositions for the substrate include alumina, at least one alkali metal, and in some embodiments, greater than 50 mol.% SiO ₂ , and in other embodiments, at least 58 mol.% SiO _2. , And in another embodiment, at least 60 mol.% SiO ₂ , wherein a ratio ((Al ₂ O ₃ + B ₂ O ₃ ) / modifier)> 1, wherein the ratios are expressed in mol% , The modifier is an alkali metal oxide. The glass composition, in certain embodiments, comprises: 58-72 mol.% SiO ₂ ; 9-17 mol.% Al ₂ O ₃ ; 2-12 mol.% B ₂ O ₃ ; 8-16 mol.% Na ₂ O; And 0-4 mol.% K ₂ O, where ratio ((Al ₂ O ₃ + B ₂ O ₃ ) / modifier)> 1.

In another embodiment, the substrate may comprise an alkali aluminosilicate glass composition comprising: 64-68 mol.% SiO ₂ ; 12-16 mol.% Na ₂ O; 8-12 mol.% Al ₂ O ₃ ; 0-3 mol.% B ₂ O ₃ ; 2-5 mol.% K ₂ O; 4-6 mol.% MgO; And 0-5 mol.% CaO.

In alternative embodiments, the substrate may comprise an alkali aluminosilicate glass composition comprising: at least 2 mol% Al ₂ O ₃ and / or ZrO ₂ , or at least 4 mol% Al ₂ O ₃ and / Or ZrO ₂ .

The reinforced substrates disclosed herein can be chemically strengthened by an ion exchange process. In the ion-exchange process, by immersion of the glass or glass ceramic substrate in the molten salt bath for a predetermined period of time, the ions at or near the glass or glass ceramic substrate are typically larger than the salt bath. Exchanged for metal ions. In one embodiment, the temperature of the molten salt bath is about 400-430 ° C. and the predetermined period of time is about 4 to about 12 hours. Incorporation of larger ions into the glass or glass ceramic substrate strengthens the substrate by creating compressive stress at or near the surface of the substrate and in the vicinity of the surface region. Corresponding tensile stresses are induced in an area or central area away from the surface of the substrate to balance the compressive stress. Glass or glass ceramic substrates using the strengthening process may be described more specifically as chemically strengthened or ion-exchanged glass or glass ceramic substrates.

In one embodiment, sodium ions in the strengthened glass or glass ceramic substrate are replaced by potassium ions with a molten bath, such as a potassium nitrate salt bath, and other alkali metal ions with other larger atomic radii such as rubidium or cesium. It can replace smaller alkali metal ions in this glass. According to certain embodiments, smaller alkali metal ions in the glass or glass ceramics may be replaced by Ag + ions to provide an antimicrobial effect. Similarly, other alkali metal salts such as, but not limited to, sulfates, phosphates, halides and the like can be used in the ion exchange process.

In a strengthened glass-based substrate, there is a stress profile on the surface where there is a compressive stress (CS) and a tension (center tensile or CT) in the center of the glass. Substitution of smaller ions by larger ions below the temperature at which the glass network can be relaxed produces a distribution of ions across the surface of the reinforced substrate that results in a stress profile. The larger volume of incoming ions produces a compressive stress (CS) on the surface and a tension (central tension, or CT) in the center of the reinforced substrate. Compressive stress (including surface CS) is described by Orihara Industrial Co., Ltd. It is measured by a surface stress meter (FSM) using a commercially available instrument, such as FSM-6000, manufactured by (Japan). Surface stress measurements depend on accurate measurement of the stress optical coefficient (SOC), which is related to the birefringence of the glass. SOC is measured according to process C (glass disk method) described in ASTM standard C770-16 of the name, "Standard Test Method for Measurement of Glass Stress-Optical Coefficient", which is incorporated herein by reference in its entirety. Included in In at least one embodiment, the glass-based substrate used for the core and / or cladding is at least 750 MPa, for example at least 800 MPa, at least 850 MPa, at least 900 MPa, at least 950 MPa, at least 1000 MPa, 1150 MPa. Or more, or have a surface compressive stress of 1200 MPa.

As used herein, DOC means the depth at which the stress in the chemically strengthened alkali aluminosilicate glass article described herein changes from compression to tensile. DOC can be measured by FSM or Scattered Light Polarizer (SCALP) according to ion exchange treatment. If the stress in the glass article is generated by exchanging potassium ions into the glass article, FSM is used to measure the DOC. If the stress is generated by exchanging sodium ions in the glass article, SCALP is used to measure the DOC. If the stress in the glass article is generated by exchanging both potassium and sodium in the glass, DOC is measured by SCALP, which indicates that the exchange depth of sodium represents DOC, and that the exchange depth of potassium ions varies in magnitude of compressive stress ( However, it is believed that it is not a change in stress from compression to tension). The exchange depth of potassium ions in these glass articles is measured by FSM.

The refractive near-field (RNF) method or SCALP can be used to measure the stress profile. If the RNF method is used to measure the stress profile, the maximum CT value provided by the SCALP is used in the RNF method. In particular, the stress profile measured by the RNF is corrected to the maximum CT value provided by the SCALP and force balanced. The RNF method is disclosed in US Pat. No. 8,854,623, entitled “Systems and Methods for Measuring Profile Properties of Glass Samples,” which is incorporated herein by reference in its entirety. In particular, the RNF method measures the amount of power in the polarized-switched light beam and generates a polarized-switched reference signal, the flattened-switched light beam switched between orthogonal polarization at a speed between 1 Hz and 50 Hz. Positioning the glass article adjacent to the reference block, wherein the measured amount of power in each orthogonal polarization is within 50% of each other. The method comprises a signal photodetector that transmits a polarized-switched light beam through a reference block and a glass sample at different depths into the glass sample and then generates the polarized-switched detector signal through the transmitted polarized-switched light beam. Relaying to the signal photodetector using the relay optical system having the same. The method also includes forming a normalized detector signal by dividing the detector signal by a reference signal and determining a profile characteristic of the glass sample from the normalized detector signal.

Examples of the glass composition are as described above. In certain embodiments, the glass compositions disclosed in US Pat. No. 9,156,724 (“'724 Patent”) can be used to use glass substrates. The '724 patent describes alkali aluminosilicate glasses that are resistant to damage due to sharp impacts and are capable of fast ion exchange. Examples of such alkali aluminosilicate glasses include at least 4 mol% P ₂ O ₅ and, when ion exchanged, at least about 3 kgf, at least about 4 kgf, at least about 5 kgf, at least about 6 kgf or at least about 7 kgf. Has a Vickers crack initiation threshold. In one or more specific embodiments, the first reinforced substrate is at least about 4 mol% P ₂ O ₅ And an alkali aluminosilicate glass comprising 0 mol% to about 4 mol% B ₂ O ₃ , wherein the alkali aluminosilicate glass does not contain Li ₂ O, wherein: 1.3 <[P ₂ O ₅ + R ₂ O / M ₂ O ₃ ] ≤ 2.3; Where M ₂ O ₃ = Al ₂ O ₃ + B ₂ O ₃ , and R ₂ O are the sum of the monovalent cation oxides present in the alkali aluminosilicate glass. In certain embodiments, such alkali aluminosilicate glasses comprise less than 1 mol% K ₂ O, for example 0 mol% K ₂ O. In certain embodiments, such alkali aluminosilicate glasses comprise less than 1 mol% B ₂ O ₃ , for example 0 mol% B ₂ O ₃ . In certain embodiments, such alkali aluminosilicate glass is ion exchanged to a depth of layer of at least about 10 μm, wherein the alkali aluminosilicate glass has a compressive layer extending from the surface of the glass to the depth of the layer, wherein the compression The layer is under a compressive stress of at least about 300 MPa. In certain embodiments, such alkali aluminosilicate glasses are monovalent and divalent cation oxides selected from the group consisting of Na ₂ O, K ₂ O, Rb ₂ O, Cs ₂ O, MgO, CaO, SrO, BaO, and ZnO. It includes. In particular embodiments, such alkali aluminosilicate glasses include: about 40 mol% to about 70 mol% SiO ₂ ; From about 11 mol% to about 25 mol% Al ₂ O ₃ ; From about 4 mol% to about 15 mol% P ₂ O ₅ ; And from about 13 mol% to about 25 mol% Na ₂ O. Glass substrates made from the glass compositions described above may be ion-exchanged to provide the profiles described and claimed herein.

In one or more embodiments, the glass compositions described in US Patent No. 20150239775 can be used to make glass substrates that can be coated to provide a coated glass-based product as described herein. U.S. Patent No. 20150239775 describes a glass article having a compressive stress profile comprising two linear portions: a first portion having a steep slope and compressing from the shallow depth, extending from the surface to a relatively shallow depth The second part extending to the depth of.

Ion exchange processes are typically performed by immersing the glass-based product in a molten salt bath containing larger ions to be ion exchanged with smaller ions in the glass. Ion exchange processes that include, but are not limited to, the number of immersion of glass in a salt bath (or baths), immersion time, bath composition and temperature, use of multiple salt baths, and additional steps such as annealing, washing, and the like. It will be appreciated by those skilled in the art that the parameters for are generally determined by the compressive stress of the glass resulting from the strengthening operation and the composition of the layer and glass of the desired depth. By way of example, ion exchange of alkali metal-containing glass may be accomplished by immersion in at least one melt bath containing salts such as nitrates, sulfates and chlorides of larger alkali metal ions. . The temperature of the molten salt bath typically ranges from about 380 ° C. to about 450 ° C., while the immersion time ranges from about 15 minutes to about 40 hours. However, other temperatures and immersion times than those described above may also be used.

Furthermore, a non-limiting example of an ion exchange process in which glass is immersed in a multiple ion exchange bath, having a washing and / or annealing step between immersions, is a priority of US Provisional Application No. 61 / 079,995, filed July 11, 2008 Is described in US Pat. No. 8,561,429, entitled “Glass with Compression Surfaces for Consumer Applications”, issued October 22, 2013, by Douglas C. Allan et al. Enhanced by multiple successive ion exchange treatments in salt baths; US Patent No. 8,312,739 by Christopher M. Lee et al., Entitled "Dual Stage Ion Exchange for Chemical Strengthening of Glass," claiming priority of US Provisional Application No. 61 / 084,398, filed on July 29, 2008. Wherein the glass is diluted by effluent ions in the first bath and then strengthened by ion exchange by being immersed in a second bath having a smaller concentration of effluent ions than the first bath. The contents of the US Pat. Nos. 8,561,429 and 8,312,739 are incorporated herein by reference in their entirety.

The compressive stress is created by chemically strengthening the glass-based article, for example, by the ion exchange process described above, wherein the plurality of first metal ions in the outer region of the glass-based article are formed by a plurality of second Exchanged with metal ions, the outer region includes a plurality of second metal ions. Each of the first metal ions has a first ion radius, and each of the second alkali metal ions has a second ion radius. The second ion radius is greater than the first ion radius, and the presence of a larger second alkali metal ion in the outer region creates a compressive stress in the outer region.

At least one of the first metal ion and the second metal ion is an ion of an alkali metal. The first ion may be an ion of lithium, sodium, potassium and rubidium. The second metal ion may be one of sodium, potassium, rubidium and cesium provided that the second alkali metal ion has a larger ion radius than the first alkali metal ion.

The coated glass-based products described herein are products having a display (or display product) (eg, consumer electronics including mobile phones, tablets, computers, navigation systems, and the like), building products, transportation products. (E.g., automobiles, trains, aircraft, oceangoing vessels, etc.), appliances, or other products such as any product requiring some transparency, scratch-resistant, abrasion resistance, or a combination thereof. Exemplary articles including all coated glass-based articles disclosed herein are shown in FIGS. 19A and 19B. Specifically, FIGS. 19A and 19B show a housing including a front face 1904, a back face 1906, and a side face 1908; An electrical component (not shown) comprising at least a controller, a memory, and a display 1910 at or near the front of the housing, wherein the electrical component is at least partially or entirely within the housing; And a cover substrate 1912 on or in front of the housing so as to be above the display. In some embodiments, the cover substrate 1912 can include all coated glass-based articles disclosed herein.

While the foregoing description is directed to various embodiments, other and additional embodiments of the present disclosure may be devised without departing from the basic scope, the scope of which is determined by the following claims.

Claims (41)

Coated glass-based products,
A glass-based substrate facing the first and first surfaces and defining a substrate thickness t in the range of about 0.1 millimeters to 3 millimeters, the glass-based substrate extending to a depth of compression (DOC) Having a compressive region having a first compressive stress CS max at a first surface of the system substrate and a second local CS max at a depth of at least 25 μm from the first surface, wherein the glass-based substrate has a substrate Young's modulus Has a value; And
And a coating on the second surface, the coating having a coating Young's modulus value greater than the substrate Young's modulus value. The method according to claim 1,
The glass-based substrate comprises a glass-based core substrate having a first side and a second side, the glass-based core substrate comprising a glass-based first cladding substrate and a glass-based second cladding substrate Wherein the first cladding substrate is bonded to the first side and the second cladding substrate is bonded to the second side by covalent bonding. The method according to claim 2,
Wherein the core substrate comprises a first glass composition, wherein each of the first cladding substrate and the second cladding substrate comprises a second glass composition, wherein the first glass composition comprises a second glass composition; Other, coated glass-based products. The method according to claim 3,
Wherein the first glass composition has a first ion diffusivity, each of the second glass compositions has a second ion diffusivity, and the first ion diffusivity and the second ion diffusivity are different. -Based products. The method according to claim 3 or 4,
Wherein the first glass composition has a first coefficient of thermal expansion (CTE), each of the second glass compositions has a second coefficient of thermal expansion (CTE), and wherein the first CTE and the second CTE are different, Coated glass-based products. The method according to claim 5,
And the second CTE is lower than the first CTE to impart compressive stress to the first cladding substrate and the second cladding substrate. The method according to any one of claims 3 to 6,
The core substrate has a first stress profile, each of the first cladding substrate and the second cladding substrate having a second stress profile, wherein the first stress profile is different from the second stress profile, Coated glass-based products. The method according to any one of claims 3 to 7,
The first glass composition has a first Young's modulus value, the second glass composition has a second Young's modulus value, the first and second Young's modulus values are different, and the coating Young's modulus value is A coated glass-based article, which is greater than the second Young's modulus value. The method according to claim 8,
And wherein the second Young's modulus value is greater than the first Young's modulus value. The method according to claim 8,
And the second Young's modulus value is less than the first Young's modulus value. The method of claim 1, wherein
The glass-based article provides a stress profile that includes a first portion where all points comprise a relatively steep tangent and a second portion where all points comprise a relatively shallow tangent relative to the relatively steep tangent. A coated glass-based article having a compressive stress with respect to depth from the first surface. The method according to claim 11,
Wherein the ratio of the steep tangent to the relatively shallow tangent is greater than two. The method according to claim 11 or 12,
Wherein the steep tangent has an absolute value in the range of 10 MPa / micron to 20 MPa / micron and the shallow tangent has an absolute value in the range of 0.5 MPa / micron to 2 MPa / micron. The method according to any one of claims 11-13,
Wherein the coating has a coating thickness ( t _c ) in the range of about 80 nanometers to 10 micrometers. The method of claim 1, wherein
Wherein the substrate Young's modulus value ranges from 60 GPa to 80 GPa and the coating Young's modulus value ranges from 70 GPa to 400 GPa. The method of claim 1, wherein
The coated Young's modulus value is in the range of 100 GPa to 300 GPa. The method of claim 1, wherein
The coating is Al ₂ O ₃ , Mn, AlO _x N _y , Si ₃ N ₄ , SiO _x N _y , Si _u Al _v O _x N _y , diamond, diamond-like carbon, Si _x C _y , Si _x O _y C _z , ZrO ₂ , TiO _x N _y And a scratch resistant coating selected from combinations thereof. The method of claim 1, wherein
The article has a compressive stress profile with a first maximum compressive stress at the first surface sufficient to provide bending strength to prevent breakage of the glass-based article from defects resulting from the first coating. , Coated glass-based products. The method according to claim 18,
Wherein the first maximum compressive stress is in the range of 800 MPa to 1200 MPa. Coated glass-based products,
A strengthened glass-based core substrate having a first surface and a second surface;
A chemically strengthened glass-based first cladding substrate having a third surface directly bonded to the first surface to provide a first core-cladding interface; And
A chemically strengthened glass-based second cladding substrate having a fourth surface directly bonded to the second surface to provide a second core-cladding interface,
The core substrate is coupled to the first cladding substrate and the second cladding substrate without a polymer between the core substrate and the first cladding substrate and without a polymer between the core substrate and the second cladding substrate, the core substrate Includes a first glass composition, each of the first cladding substrate and the second cladding substrate comprising a second glass composition, wherein the first glass composition is different from the second glass composition, wherein The first glass composition has a first Young's modulus value, the second glass composition has a second Young's modulus value, and the glass-based article further comprises a first coating on the first cladding substrate. Wherein the first coating comprises a material selected to have a first coating Young's modulus value, wherein the first coating Young's modulus value is greater than the second Young's modulus value. The method of claim 20,
Further comprising a second coating on the second cladding substrate, the second coating comprising a material selected to have a second coating Young's modulus value, wherein the second coating Young's modulus value is the second Young's modulus value Larger, coated glass-based products. The method according to claim 20 or 21,
Wherein the reinforced core substrate is chemically strengthened and the first cladding substrate has an optimized stress profile to be resistant to breakage from deep flaws. The method according to claim 22,
The first cladding substrate has a fifth surface, and the glass-based article has a fifth surface sufficient to provide bending strength to prevent breakage of the glass-based article from defects resulting from the first coating. A coated glass-based article having a compressive stress profile with a first maximum compressive stress in. The method according to claim 23,
The first maximum compressive stress is in the range of 500 MPa to 1200 MPa coated glass-based article. The method of claim 24,
Wherein the first maximum compressive stress is in the range of 800 MPa to 1200 MPa. The method according to any one of claims 23 to 25,
And the second cladding substrate comprises a sixth surface, wherein the fifth surface and the sixth surface define a thickness in the range of about 0.1 millimeters to 3 millimeters prior to coating. The method according to any one of claims 23 to 26,
And the first coating has a thickness in the range of 5 nanometers to 5 micrometers. The method of claim 27,
And the first coating has a thickness in the range of 10 nanometers to 2 micrometers. The method according to any one of claims 23 to 28,
Wherein said first coating is selected from the group consisting of silica, indium tin oxide, aluminum oxynitride, porous silica, glass-ceramic or ceramic. The method according to any one of claims 23 to 29, wherein
And the glass-based substrate comprises an ion exchangeable alkali aluminosilicate glass composition. The method of claim 30,
And the glass-based substrate comprises an ion exchangeable alkali aluminoborosilicate glass composition. The method according to any one of claims 20 to 31,
Wherein the first cladding thickness is selected to promote stable crack growth for cracks in the range of 25 to 150 microns. A method of making a coated glass-based product, the method comprising:
Coupling the glass-based first cladding substrate to the first face of the strengthened glass-based core substrate, the first cladding substrate having a first cladding substrate Young's modulus value;
Covalently bonding a glass-based second cladding substrate to a second side of the strengthened glass-based core substrate;
Chemically strengthening the first cladding substrate and the second cladding substrate; And
Applying a coating having a coating Young's modulus value to the first cladding substrate, wherein the coating Young's modulus value is greater than the first cladding substrate Young's modulus value. The method according to claim 33,
The glass-based core substrate is chemically strengthened, and the step of chemically strengthening the first cladding substrate is performed after bonding the first cladding substrate to the core substrate, and chemically strengthening the second cladding substrate. The step of strengthening is carried out after bonding the second cladding substrate to the core substrate. The method of claim 34, wherein
The core substrate has a first bonding surface and a second bonding surface facing the first bonding surface, wherein the first cladding substrate has a third bonding surface, and the second cladding substrate is formed of a first bonding surface. Having a bonding surface of four, wherein the method comprises the core substrate, the first cladding substrate, and to provide hydroxyl groups on the first bonding surface, the second bonding surface, the third bonding surface, and the fourth bonding surface; Cleaning the second cladding substrate; And
Positioning the first bond surface to be in contact with the third bond surface and bonding the third bond surface to be positioned with the fourth bond surface to provide a laminated glass-based coating. Manufacturing method of the product. The method of claim 35, wherein
Further comprising heating the laminated stack. The method of claim 36,
The heating of the lamination stack may be performed for a time sufficient to form a covalent bond between the first bond surface and a third bond surface, and a covalent bond between the second bond surface and the fourth bond surface, and Heating to a temperature, wherein the covalent bond is formed without a polymer or an adhesive. The method of claim 36,
Heating the laminated stack to at least about 400 ° C. for a period of at least 30 minutes. The method of claim 38,
And chemically strengthening the first cladding substrate and the second cladding substrate. As consumer electronics,
A housing having a front, a back and a side;
An electrical component at least partially provided within the housing, the electrical component including at least a controller, a memory, and a display, the display being provided at or near the front of the housing; And
A consumer electronic product comprising the coated glass-based product of any one of claims 1-19. As consumer electronics,
A housing having a front, a back and a side;
An electrical component at least partially provided within the housing, the electrical component including at least a controller, a memory, and a display, the display being provided on or in front of the housing; And
A consumer electronic product comprising the coated glass-based product of claim 20.

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